CN108539102A - Nonaqueous electrolytic solution secondary battery spacer - Google Patents

Nonaqueous electrolytic solution secondary battery spacer Download PDF

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Publication number
CN108539102A
CN108539102A CN201810175247.5A CN201810175247A CN108539102A CN 108539102 A CN108539102 A CN 108539102A CN 201810175247 A CN201810175247 A CN 201810175247A CN 108539102 A CN108539102 A CN 108539102A
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China
Prior art keywords
secondary battery
electrolytic solution
nonaqueous electrolytic
solution secondary
spacer
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CN201810175247.5A
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CN108539102B (en
Inventor
有濑郎
有濑一郎
村上力
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/423—Polyamide resins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/491—Porosity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/489—Separators, membranes, diaphragms or spacing elements inside the cells, characterised by their physical properties, e.g. swelling degree, hydrophilicity or shut down properties
    • H01M50/497—Ionic conductivity
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/50—Current conducting connections for cells or batteries
    • H01M50/572—Means for preventing undesired use or discharge
    • H01M50/584—Means for preventing undesired use or discharge for preventing incorrect connections inside or outside the batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H01M50/406—Moulding; Embossing; Cutting
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of nonaqueous electrolytic solution secondary battery spacer, as the nonaqueous electrolytic solution secondary battery spacer that the low nonaqueous electrolytic solution secondary battery of resistance increment rate after charge and discharge cycles can be repeated effective for manufacture, including polyolefin porous membrane, ion is 300J/mol/ μm or more and 900J/mol/ μm or less through energy barrier.

Description

Nonaqueous electrolytic solution secondary battery spacer
Technical field
The present invention relates to nonaqueous electrolytic solution secondary battery spacer, nonaqueous electrolytic solution secondary battery component and non-water power Solve liquid secondary battery.
Background technology
The nonaqueous electrolytic solution secondary batteries such as lithium secondary battery are at present by whole as PC, portable phone and mobile information Battery or vehicle-mounted battery used in the equipment such as end are widely used.
It is implemented in the equipment for carrying lithium ion battery and a variety of electrical resistance protection electricity is set in charger, battery pack Road, so that battery is normal, the countermeasure that safely acts, however for example when because the failure of these protection circuits or due to malfunction to lithium When ion battery persistently charges, will occur along with the electrolyte in exothermic positive and negative pole surface redox decompose, by Oxygen releasing and the precipitation of the lithium metal in cathode, are finally absorbed in thermal runaway state caused by the decomposition of positive active material, To have the danger caught fire, ruptured for causing battery sometimes.
In order to stop with making cell safety before the thermal runaway state for reaching such danger, at present most lithium from In sub- battery, use porous substrate using the polyolefin with closing function as principal component as spacer, the closing work( Can be opened in porous substrate at about 130 DEG C~140 DEG C when making internal temperature of battery increase because of certain not good situation Pore will occlude.By showing the function when internal temperature of battery increases, so that it may with block through spacer from Son stops with making cell safety.
It is public as the porous substrate that may be used as nonaqueous electrolytic solution secondary battery spacer, such as in patent document 1 A kind of microporous polyethylene film was opened, for being maintained film thickness and the porosity necessary to embodying intensity, realize high ion Bending rate, the porosity and average pore size are set as specific range by the purpose of permeability.
Existing technical literature
Patent document
Patent document 1：Japanese Laid-Open Patent Publication " Unexamined Patent 11-130900 bulletins (on May 18th, 1999 is open) "
Invention content
Problem to be solved by the invention
Has the previous nonaqueous electrolytic solution secondary battery being made of perforated membrane in as disclosed in Patent Document 1 With the increasing for the resistance (electrode resistance) in the nonaqueous electrolytic solution secondary battery of spacer, being repeated after above-mentioned charge and discharge cycles Add rate high, cycle characteristics is insufficient.
The method for solving problem
Thus, the inventors of the present invention are conceived to the nonaqueous electrolytic solution secondary battery spacer being not concerned in the past (to be had below When be referred to as " spacer ") ion through energy barrier and have the non-aqueous solution electrolysis of above-mentioned nonaqueous electrolytic solution secondary battery spacer The relationship of the resistance increment rate after charge and discharge cycles is repeated in liquid secondary battery.It is thus been found that having per unit film thickness Ion through energy barrier the spacer of specific range nonaqueous electrolytic solution secondary battery after charge and discharge cycles are repeated Resistance increment rate is low, and cycle characteristics is excellent, to come up with the present invention.
The present invention includes to be invented shown in [1] below~[4].
[1] a kind of nonaqueous electrolytic solution secondary battery spacer is the non-aqueous electrolyte secondary for including polyolefin porous membrane Battery spacer,
The ion of per unit film thickness is 300J/mol/ μm or more and 900J/mol/ μm or less through energy barrier.
[2] the nonaqueous electrolytic solution secondary battery spacer as described in [1], the polyolefin porous membrane one side or Two sides has insulating properties porous layer.
[3] a kind of nonaqueous electrolytic solution secondary battery component, it is non-aqueous described in positive, [1] or [2] to configure in order Electrolyte secondary batteries are formed with spacer and cathode.
[4] a kind of nonaqueous electrolytic solution secondary battery has the nonaqueous electrolytic solution secondary battery described in [1] or [2] and uses Spacer.
Invention effect
The nonaqueous electrolytic solution secondary battery of an embodiment of the invention is had the following effect with spacer, that is, After charge and discharge cycles are repeated in the nonaqueous electrolytic solution secondary battery for having nonaqueous electrolytic solution secondary battery spacer Resistance increment rate is low, and cycle characteristics is excellent.
Specific implementation mode
An embodiment of the invention is described as follows, however the present invention is not so limited.The present invention is not by following Each composition for illustrating limits, and can be made various changes in the range shown in the range of technical solution, for will be different Embodiment obtained by disclosed technical method is appropriately combined respectively in embodiment is also contained in the technical scope of the present invention In.As long as it should be noted that be not specifically stated in the present specification, indicate " A~B " of numberical range mean that " A with Upper and B or less ".
[embodiment 1]
The nonaqueous electrolytic solution secondary battery of embodiments of the present invention 1 is non-aqueous comprising polyolefin porous membrane with spacer Electrolyte secondary batteries spacer, it is 300J/mol/ μm or more and 900J/mol/ μm that the ion of per unit film thickness, which penetrates energy barrier, Below.
The nonaqueous electrolytic solution secondary battery of embodiments of the present invention 1 with spacer include polyolefin porous membrane, preferably by Polyolefin porous membrane is constituted.Herein, so-called " polyolefin porous membrane " is the perforated membrane using polyolefin-based resins as principal component.Separately Outside, it is that composition is more that so-called " using polyolefin-based resins as principal component ", which refer to polyolefin-based resins ratio shared in perforated membrane, The 50 volume % or more, preferably 90 volume % or more, more preferably 95 volume % or more of the material entirety of pore membrane.
Said polyolefins perforated membrane can become between the nonaqueous electrolytic solution secondary battery use of an embodiment of the invention The base material of spacing body.In addition, said polyolefins perforated membrane has multiple pores linked inside it, gas, liquid can be made Pass through from one towards another face.
It is more preferably 3 × 10 comprising weight average molecular weight in said polyolefins system resin5~15 × 106High molecular weight at Point.Especially if the high molecular weight components for being 1,000,000 or more comprising weight average molecular weight in polyolefin-based resins, then above-mentioned poly- The porous film strength of alkene improves, therefore more preferably.
The polyolefin-based resins of principal component as said polyolefins perforated membrane are not particularly limited, for example, making The monomers (co) polymerizations such as ethylene, propylene, 1- butylene, 4-methyl-1-pentene, 1- hexenes are formed for thermoplastic resin Homopolymer (such as polyethylene, polypropylene, polybutene) or copolymer (such as ethylene-propylene copolymer).
Polyolefin porous membrane can be individually include these polyolefin-based resins layer or comprising these polyolefin-based resins Layer of more than two kinds.Wherein, since (closing) super-high-current can be prevented to flow through at lower temperatures, preferred polyethylene, The particularly polyethylene of the high molecular weight more preferably based on ethylene.It should be noted that polyolefin porous membrane can also be It does not damage in the range of the function of this layer comprising the ingredient other than polyolefin.
As polyethylene, low density polyethylene (LDPE), high density polyethylene (HDPE), linear polyethylene (ethene-alpha-olefin can be enumerated Copolymer), the ultra-high molecular weight polyethylene etc. that weight average molecular weight is 1,000,000 or more, wherein further preferred weight average molecular weight is 1000000 or more ultra-high molecular weight polyethylene is particularly preferably 5 × 10 comprising weight average molecular weight5~15 × 106High molecular weight Ingredient.
The film thickness of said polyolefins perforated membrane is not particularly limited, however preferably 4~40 μm, more preferably 5~20 μm.
If the film thickness of said polyolefins perforated membrane is 4 μm or more, the internal short-circuit of battery can be fully prevented, from The viewpoint considers preferred.
On the other hand, if the film thickness of said polyolefins perforated membrane be 40 μm hereinafter, if can prevent nonaqueous electrolytic solution two The enlargement of primary cell considers preferred from the viewpoint.
For the weight per unit area of the per unit area of said polyolefins perforated membrane, in order to which the weight of battery can be improved Energy density, volume energy density, it is often preferred that 4~20g/m2, more preferably 5~12g/m2。
For the air permeability of said polyolefins perforated membrane, from the viewpoint of showing sufficient ion permeability, with Gurley value meters are preferably 30~500sec/100mL, more preferably 50~300sec/100mL.
For the voidage of said polyolefins perforated membrane, in order to which the maintenance dose of electrolyte can be improved, and can obtain The function that can reliably prevent (closing) super-high-current to flow through at lower temperatures, the preferably 20 volume % of volume %~80, More preferably 30~75 volume %.
For the aperture of pore possessed by said polyolefins perforated membrane, from sufficient ion permeability and structure is prevented From the viewpoint of entrance at the particle of electrode, preferably 0.3 μm hereinafter, more preferably 0.14 μm or less.
The ion of above-mentioned per unit film thickness is the value obtained as follows through energy barrier, that is, dynamic in nonaqueous electrolytic solution secondary battery It, will be as the ion of charge carrier (such as Li when making+) by nonaqueous electrolytic solution secondary battery spacer when activation energy (energy Build) divided by the spacer film thickness and obtain.
In the case where the ion of above-mentioned per unit film thickness is small through energy barrier, it may be said that ion is easy in above-mentioned spacer Through.That is, it can be said that the interaction of the resin wall and charge carrier inside spacer is weak.On the other hand, in above-mentioned per unit The ion of film thickness through energy barrier it is big in the case of, it may be said that ion is difficult to penetrate in above-mentioned spacer.That is, it can be said that spacer The interaction of internal resin wall and charge carrier is strong.
In the nonaqueous electrolytic solution secondary battery spacer of an embodiment of the invention, by making per unit film thickness Ion through energy barrier be 300J/mol/ μm or more and 900J/mol/ μm hereinafter, can the non-aqueous electrolyte secondary enclosed When the nonaqueous electrolytic solution secondary battery action of battery spacer, the nonaqueous electrolytic solution two will be penetrated as the ion of charge carrier The speed control of primary cell spacer is appropriate speed.
It is believed that between the above-mentioned ion ion too low, above-mentioned through energy barrier is used through nonaqueous electrolytic solution secondary battery In the case of the excessive velocities of spacing body, after charge and discharge cycles are repeated, above-mentioned ion is exhausted in electrode (anode), thus Make electrode degradation, the resistance increment rate after charge and discharge cycles is repeated and becomes larger.
Thus, it is 300J/mol/ μm or more by making the ion of per unit film thickness penetrate energy barrier, above-mentioned electricity can be prevented The deterioration of pole makes that the resistance increment rate reduction after charge and discharge cycles is repeated.Consider from the viewpoint, the ion of per unit film thickness It is preferably 320J/mol/ μm or more through energy barrier, more preferably 350J/mol/ μm or more.
On the other hand, excessively high through energy barrier in above-mentioned ion, in the case that permeability of above-mentioned ion is too low, repeatedly After carrying out charge and discharge cycles, above-mentioned ion by when thermal stress that nonaqueous electrolytic solution secondary battery spacer is applied and mechanics Stress becomes larger, as a result, the internal structure (pore structure) of the nonaqueous electrolytic solution secondary battery spacer changes, therefore repeatedly The resistance increment rate after charge and discharge cycles is carried out to become larger.
Furthermore it is possible to think, in the case where above-mentioned ion is excessively high through energy barrier, between which uses The polarity of the resin wall of spacer inside is excessively high.At this point, it is non-to have coming from of being generated when nonaqueous electrolytic solution secondary battery acts The high by-product of the polarity of water electrolysis liquid blocks the gap of nonaqueous electrolytic solution secondary battery spacer, increases charge and discharge is repeated Electricity cycle after resistance increment rate the case where.
Thus, consider from the viewpoint, the ion of per unit film thickness is preferably 800J/mol/ μm hereinafter, more excellent through energy barrier It is selected as 780J/mol/ μm or less.
The ion of the per unit film thickness of the nonaqueous electrolytic solution secondary battery spacer of an embodiment of the invention is saturating Crossing energy barrier is calculated using method as shown below.
First, the nonaqueous electrolytic solution secondary battery of an embodiment of the invention is cut into φ 17mm's with spacer It is discoid, it is sandwiched with the SUS plates of 2 thickness 0.5mm, φ 15.5mm, injects electrolyte and button cell (CR2032 types) is made.On Electrolyte is stated to use in ethylene carbonate (EC)/methyl ethyl carbonate (EMC)/diethyl carbonate (DEC)=3/5/2 (volume ratio) In the mixed solvent is so that LiPF6Concentration reach 1mol/L mode be dissolved with LiPF6Solution.
Then, by made button cell be set to it is aftermentioned be set as in the thermostat of given temperature, use Solartron corporation AC impedance devices (FRA1255B) and CellTest systems (1470E), frequency 1MHz~0.1Hz, Nyquist diagram is calculated under amplitude 10mV, the liquid resistance (liquid resistance) of spacer at each temperature is found out according to the value of X intercepts r0, calculate ion using following formulas (1) and (2) and penetrate energy barrier.The temperature of thermostat be set as 50 DEG C, 25 DEG C, 5 DEG C, -10 ℃。
Herein, ion is indicated through energy barrier following formula (1).
K=1/r0=Aexp (- Ea/RT) (1)
Ea：Ion penetrates energy barrier (J/mol)
k：Reaction constant
r0：Liquid resistance (Ω)
A：Frequency factor
R：Gas constant=8.314J/mol/K
T：The temperature (K) of thermostat
When the natural logrithm on the both sides of modus ponens (1), that is, become following formula (2).Based on the formula (2), to the inverse of temperature Draw ln (1/r0), and find out as by the drafting desire to make money or profit the straight line obtained with least square method slope-Ea/R ,- It is multiplied by gas constant R in the value of Ea/R and calculates Ea.Thereafter, by the Ea of calculating divided by the film thickness of spacer, per unit film is calculated Thick ion penetrates energy barrier.
Ln (1/k)=ln (1/r0)=lnA-Ea/RT (2)
The film thickness of above-mentioned spacer is not particularly limited, however preferably 4~40 μm, more preferably 5~20 μm.
If the film thickness of above-mentioned spacer is 4 μm or more, the internal short-circuit of battery can be fully prevented, from the viewpoint Consider preferred.
On the other hand, if the film thickness of above-mentioned spacer be 40 μm hereinafter, if can prevent nonaqueous electrolytic solution secondary battery Enlargement, consider from the viewpoint preferred.
For the weight per unit area of the per unit area of above-mentioned spacer, in order to which the weight energy that can improve battery is close Degree, volume energy density, it is often preferred that 4~20g/m2, more preferably 5~12g/m2。
For the air permeability of above-mentioned spacer, from the viewpoint of showing sufficient ion permeability, with Gurley values Meter is preferably 30~500sec/100mL, more preferably 50~300sec/100mL.
For the voidage of above-mentioned spacer, in order to improve the maintenance dose of electrolyte, and can obtain can be The function of reliably preventing (closing) super-high-current to flow through under lower temperature, the preferably 20 volume % of volume %~80, more preferably For 30~75 volume %.
For the aperture of pore possessed by above-mentioned spacer, from sufficient ion permeability and prevent from constituting electrode Particle entrance from the viewpoint of, preferably 0.3 μm hereinafter, more preferably 0.14 μm or less.
The nonaqueous electrolytic solution secondary battery spacer of an embodiment of the invention can also be more in said polyolefins Other than pore membrane, it is further equipped with refractory layer or adhesive linkage, protective layer etc. as needed.
[manufacturing method of polyolefin porous membrane]
The manufacturing method of said polyolefins perforated membrane is not particularly limited, for example, following method, that is, will gather Olefin-based resin, Petropols and plasticizer squeeze out after being kneaded, and the polyolefine resin composition of sheet is thus made, and stretching should After polyolefine resin composition, heat fixation is dried in part or all that plasticizer is removed with solvent appropriate.
Specifically, method as shown below can be enumerated.
(A) polyolefin-based resins and Petropols are added in kneading machine and carry out melting mixing, obtain molten mixture Process；
(B) it adds plasticizer into the molten mixture of gained and is kneaded, obtain polyolefine resin composition Process；
(C) polyolefine resin composition of gained is squeezed out from the T shape die heads of extruder, is configured to while cooling down Sheet, the process for obtaining the polyolefine resin composition of sheet；
(D) process for stretching the polyolefine resin composition of the sheet of gained；
(E) process for using cleaning solution to clean stretched polyolefine resin composition；
(F) heat fixation is dried to the polyolefine resin composition through over cleaning, thus obtains polyolefin porous membrane Process.
In process (A), for the usage amount of polyolefin-based resins, by the weight of the polyolefine resin composition of gained In the case of being set as 100 weight %, the preferably 6 weight % of weight %~45, more preferably 9 weight of weight %~36 %.
As Petropols, can enumerate poly- by main material of the C5 such as isoprene, amylene and pentadiene petroleum distillates Aliphatic hydrocarbon resin obtained by conjunction；With the C9 such as indenes, vinyltoluene and methyl styrene petroleum distillates for main polymerizable raw material and The aromatic hydrocarbon resin obtained；Their copolymer resins；By alicyclic saturated hydrocarbon resin obtained by above-mentioned hydrogenate resins；And they Mixture.Petropols are preferably alicyclic saturated hydrocarbon resin.Above-mentioned Petropols due to having multiple be easy in the structure The unsaturated bond or tertiary carbon of free radical are generated, therefore with the feature being oxidized easily.
By the way that Petropols are mixed into polyolefine resin composition, can adjust gained polyolefin porous membrane inside Resin wall and charge carrier interaction.I.e., it is possible to which the ion for being suitably adjusted spacer penetrates energy barrier.
It is used as the Petropols of the ingredient of oxidation easier than polyolefin-based resins by mixing, it can be by the polyolefin of gained Resin wall inside perforated membrane moderately aoxidizes, that is, compared with the case where being added without Petropols, is adding Petropols In the case of, the ion of the spacer of gained becomes larger through energy barrier.
It is preferable to use the resins that softening point is 90 DEG C~125 DEG C for above-mentioned Petropols.Use for above-mentioned Petropols Amount, in the case where the weight of the polyolefine resin composition of gained is set as 100 weight %, preferably 0.5 weight %~40 Weight %, more preferably 1 weight of weight %~30 %.
As plasticizer, it is unsaturated advanced that the phthalates such as dioctyl phthalate, oleyl alcohol etc. can be enumerated Alcohol, paraffin or stearyl alcohol etc. are saturated higher alcohol and atoleine etc..
In process (B), by plasticizer be added kneading machine when kneading machine inside temperature be preferably 135 DEG C or more and 200 DEG C hereinafter, more preferably 140 DEG C or more and 170 DEG C or less.
It, can be by polyolefin-based resins and oil tree by controlling the temperature inside kneading machine in above-mentioned range Plasticizer is added in the state of being suitably mixed in fat.As a result, it is possible to more suitably obtain polyolefin-based resins and stone The effect of oleoresin mixing.
For example, if be added plasticizer when kneading machine inside temperature it is too low, can not be by polyolefin-based resins and stone Oleoresin uniformly mixes, and has the case where can not moderately aoxidizing the resin wall inside polyolefin porous membrane.On the other hand, exist In the case that above-mentioned temperature is excessively high (such as 200 DEG C or more), the case where having the heat deterioration for causing resin.
It stretches and can only carry out in the MD direction in process (D), can also only be carried out on the directions TD, it can also be in MD Direction is carried out in the both direction of the directions TD.As the method stretched on the directions MD and the directions TD both direction, can enumerate It stretches in the MD direction and followed by be pulled up gradually biaxial stretch-formed of the side TD and is carried out at the same time the directions MD and the directions TD It is biaxial stretch-formed while stretching.
When stretching, can use with chuck clamp sheet polyolefine resin composition end come the method elongated, The method elongated by transporting the rotating speed of the roller of the polyolefine resin composition of sheet by change can also be used, can also be used Roll the method for the polyolefine resin composition of sheet using a pair of rolls.
In process (D), the stretching ratio when polyolefine resin composition of above-mentioned sheet is stretched in the MD direction is excellent 3.0 times or more and 7.0 times are selected as hereinafter, more preferably 4.5 times or more and 6.5 times or less.It will be stretched in the MD direction Stretching ratio of the polyolefine resin composition of sheet again when the side TD is pulled up be preferably 3.0 times or more and 7.0 times hereinafter, More preferably 4.5 times or more and 6.5 times or less.
Draft temperature is preferably 130 DEG C hereinafter, more preferably 110 DEG C~120 DEG C.
In process (E), as long as cleaning solution can remove the solvent of plasticizer etc., there is no particular limitation, for example may be used To enumerate the halogen such as the aliphatic hydrocarbons such as heptane, octane, nonane, decane, dichloromethane, chloroform, dichloroethanes, 1,2- dichloropropanes For hydrocarbon etc..
In process (F), it is heat-treated in specific temperature by the polyolefine resin composition to having cleaned, and into The dry heat fixation of row.
Dry heat fixation is typically under air using progress such as throughcirculation dryer or heating rollers.
From the further degree of oxidation for finely tuning the resin wall inside polyolefin porous membrane, properly control polyolefin porous membrane From the viewpoint of the interaction of internal resin wall and charge carrier, preferably 100 DEG C or more and 150 DEG C or less, it is more preferable At 110 DEG C or more and 140 DEG C or less, further preferably in 120 DEG C or more the and 135 DEG C above-mentioned dry heat of temperature implementation below It is fixed.Additionally, it is preferred that with 1 minute or more and 60 minutes or less, more preferably with 1 minute or more and 30 minutes time below come into The above-mentioned dry heat fixation of row.
[embodiment 2]
The nonaqueous electrolytic solution secondary battery spacer of embodiments of the present invention 2 is in the non-of embodiments of the present invention 1 The one or both sides of polyolefin porous membrane in water electrolysis liquid secondary battery spacer have insulating properties porous layer.Thus, this The nonaqueous electrolytic solution secondary battery lamination spacer of the embodiment 2 of invention includes the implementation for constituting the present invention recorded above The polyolefin porous membrane of the nonaqueous electrolytic solution secondary battery spacer of mode 1.Hereinafter, sometimes by embodiments of the present invention 2 Nonaqueous electrolytic solution secondary battery be known as " laminated body " with spacer.
[insulating properties porous layer]
The insulating properties for constituting the nonaqueous electrolytic solution secondary battery lamination spacer of an embodiment of the invention is porous Layer is usually comprising resin layer, preferably refractory layer or adhesive linkage made of resin.Constitute insulating properties porous layer (below also referred to as For " porous layer ") resin be preferably insoluble in the electrolyte of battery, in addition, in the use scope of the battery in electrochemistry Stablize.
Porous layer is laminated in the one or both sides of nonaqueous electrolytic solution secondary battery spacer as needed.It is more in polyolefin In the case of the one side stacking porous layer of pore membrane, which is preferably laminated in polyene when nonaqueous electrolytic solution secondary battery is made The face facing with anode of hydrocarbon perforated membrane, is more preferably laminated in the face contacted with anode.
As the resin for constituting porous layer, for example, polyolefin；(methyl) acrylic ester resin；Fluorine-containing tree Fat；Polyamide series resin；Polyimides system resins；Polyester based resin；Rubber；Fusing point or glass transition temperature are 180 DEG C Above resin；Water-soluble polymer etc..
It is preferred polyolefm, polyester based resin, acrylic ester resin, fluorine resin, polyamide-based in above-mentioned resin Resin and water-soluble polymer.As polyamide series resin, preferably fully aromatic polyamide (aromatic polyamide resin).As poly- Ester system resin, preferably polyarylate and liquid crystal polyester.
Porous layer can also include particle.So-called particle in this specification is the organic fine particles of generally known as filler Or inorganic particles.Thus, in the case where porous layer includes particle, above-mentioned resin contained in porous layer has micro- as making Between grain and the function as binder resin of particle and perforated membrane bonding.In addition, the above-mentioned preferred insulating properties of particle is micro- Grain.
As organic fine particles contained in porous layer, the resiniferous particle of packet can be enumerated.
As inorganic particles contained in porous layer, specifically, for example, comprising calcium carbonate, talcum, clay, It is kaolin, silica, hydrotalcite, diatomite, magnesium carbonate, barium carbonate, calcium sulfate, magnesium sulfate, barium sulfate, aluminium hydroxide, vigorous Nurse stone, magnesium hydroxide, calcium oxide, magnesia, titanium oxide, titanium nitride, aluminium oxide (alumina), aluminium nitride, mica, zeolite and The filler of the inorganic matters such as glass.These inorganic particles are insulating fine particles.Above-mentioned particle can be used only a kind, can also combine Use two or more.
In above-mentioned particle, the particle of inorganic matter is preferably comprised, more preferably includes silica, calcium oxide, magnesia, oxygen Change the particle of the inorganic oxides such as titanium, aluminium oxide, mica, zeolite, aluminium hydroxide or boehmite, is further preferably selected from dioxy At least one kind of particle in SiClx, magnesia, titanium oxide, aluminium hydroxide, boehmite and aluminium oxide, particularly preferred aluminium oxide.
The content of particle in porous layer is preferably 1~99 volume % of porous layer, more preferably 5~95 volume %.It is logical It crosses and the content of particle is set as above range, the gap formed by the contact between particle will by the case where blockings such as resin It tails off.Thus, it is possible to obtain sufficient ion permeability, and the weight per unit area of per unit area can be made to be appropriate Value.
Particle or different from each other two or more of specific surface area can also be applied in combination in particle.
The thickness of porous layer is preferably 0.5~15 μm, more preferably 2~10 μm in each layer.
If the thickness of porous layer is less than 1 μm, there will be being unable to fully prevent internal as caused by waiting the breakage of battery The situation of short circuit.In addition, the case where having the maintenance dose reduction of the electrolyte in porous layer.On the other hand, if porous layer Thickness with regard to two sides it is total for be more than 30 μm, reduced there will be multiplying power property or cycle characteristics the case where.
The weight per unit area (each layer) of the per unit area of porous layer is preferably 1~20g/m2, more preferably 4~ 10g/m2。
In addition, the volume (each layer) of porous layer constituent contained in every 1 square metre of porous layer be preferably 0.5~ 20cm3, more preferably 1~10cm3, further preferably 2~7cm3。
For the voidage of porous layer, in order to which sufficient ion permeability, preferably 20~90 volume % can be obtained, more Preferably 30~80 volume %.In addition, for the aperture of pore possessed by porous layer, it is abundant in order to which laminated body can be made to obtain Ion permeability, preferably 3 μm hereinafter, more preferably 1 μm or less.
The film thickness of the laminated body of an embodiment of the invention is preferably 5.5 μm~45 μm, more preferably 6 μm~25 μ m。
The air permeability of the laminated body of an embodiment of the invention is preferably 30~1000sec/ in terms of Gurley values 100mL, more preferably 50~800sec/100mL.
It should be noted that the laminated body of an embodiment of the invention can also said polyolefins perforated membrane and absolutely Other than edge porous layer, also according to needs comprising refractory layer or adhesive linkage, protection in the range for not damaging the purpose of the present invention Perforated membrane (porous layer) well known to layer etc..
The laminated body of an embodiment of the invention has to be used with the nonaqueous electrolytic solution secondary battery of the above embodiment 1 The ion of the per unit film thickness of the identical specific range of spacer penetrates energy barrier.Thus, it is possible to make non-comprising the laminated body The resistance increment rate reduction of water electrolysis liquid secondary battery being repeated after charge and discharge cycles, improves cycle characteristics.The laminated body The ion of per unit film thickness can for example be controlled by following manner through energy barrier, that is, by the above method to the layer The ion of the per unit film thickness for the polyolefin porous membrane for including in stack is adjusted through energy barrier.
[manufacturing method of laminated body]
The manufacturing method of laminated body as an embodiment of the invention, for example, by by aftermentioned painting Cloth liquid is coated on the surface of polyolefin porous membrane and is allowed to method that is dry and making insulating properties porous layer be precipitated.
It should be noted that before the surface by above-mentioned coating solution in polyolefin porous membrane, it can be right as needed The surface of the applied coating solution of the polyolefin porous membrane carries out hydrophilicity-imparting treatment.
Coating fluid used in the manufacturing method of the laminated body of an embodiment of the invention usually can be by making The resin that can include in above-mentioned porous layer is dissolved in solvent and makes the particle that can include in above-mentioned porous layer point It dissipates and prepares.Herein, the fat-solvent solvent of tree is made to double as the decentralized medium for making particle disperse.Herein, resin can not also dissolve It is included in above-mentioned coating fluid as lotion in solvent.
Above-mentioned solvent (decentralized medium) as long as harmful effect will not be caused to polyolefin porous membrane, can be uniformly and steady Surely dissolve above-mentioned resin, uniformly and steadily disperse above-mentioned particle, be not particularly limited.(divide as above-mentioned solvent Dispersion media), specifically, for example, water and organic solvent.Above-mentioned solvent can be used only a kind, and can also combine makes Use two or more.
As long as coating fluid can meet for obtain desired porous layer and required resin solid content (resin is dense Degree) or the conditions such as particulate loading, then no matter can using which kind of method formation.As the forming method of coating fluid, specifically, For example, mechanical mixing method, ultrasonic dispersion, good pressure distribution method, medium dispersing method etc..In addition, above-mentioned coating fluid It can be in the range for not damaging the purpose of the present invention, as the ingredient other than above-mentioned resin and particle, including dispersant or increasing Mould the additives such as agent, surfactant, pH adjusting agent.As long as it should be noted that the additive amount of additive does not damage this hair The range of bright purpose.
Porous layer is formed for coating method of the coating fluid on polyolefin porous membrane, i.e. on the surface of polyolefin porous membrane Method be not particularly limited.As the forming method of porous layer, for example, coating fluid is directly coated at polyolefin Behind the surface of perforated membrane, the method for removing solvent (decentralized medium)；By coating solution on supporter appropriate, solvent is removed (decentralized medium) and after forming porous layer, so that the porous layer is crimped with polyolefin porous membrane, the method for then divesting supporter；It will Coating solution makes polyolefin porous membrane be crimped on coated face after on supporter appropriate, then divests supporter, removes later Go the method etc. of solvent (decentralized medium).
As the coating method of coating fluid, known method may be used, specifically, for example, intaglio plate Rubbing method, dip coating, stick coating method and die coating method etc..
The removing method of solvent (decentralized medium) is usually by dry method.Alternatively, it is also possible to by institute in coating fluid The solvent (decentralized medium) contained is dried after being replaced into other solvents.
[embodiment 3：Nonaqueous electrolytic solution secondary battery component, embodiment 4：Nonaqueous electrolytic solution secondary battery]
The nonaqueous electrolytic solution secondary battery of embodiments of the present invention 3 configures in order the implementation of anode, the present invention with component The nonaqueous electrolytic solution secondary battery of mode 1 or 2 is formed with spacer and cathode.
The nonaqueous electrolytic solution secondary battery of embodiments of the present invention 4 includes the non-water power of embodiments of the present invention 1 or 2 Solve liquid secondary battery spacer.
The nonaqueous electrolytic solution secondary battery of an embodiment of the invention is, for example, to go doping to obtain using the doping of lithium The non-aqueous secondary battery for obtaining electromotive force can have and stack gradually positive, an embodiment of the invention non-aqueous solution electrolysis Nonaqueous electrolytic solution secondary battery component made of liquid secondary battery spacer and cathode.In addition, one embodiment of the present invention The nonaqueous electrolytic solution secondary battery of formula for example can be the secondary electricity of non-water system that doping acquisition electromotive force is removed using the doping of lithium Pond, and for have stack gradually anode, porous layer, an embodiment of the invention nonaqueous electrolytic solution secondary battery use between The lithium rechargeable battery of nonaqueous electrolytic solution secondary battery component made of spacing body and cathode, that is, have stack gradually anode, Nonaqueous electrolytic solution secondary battery made of the nonaqueous electrolytic solution secondary battery of embodiments of the present invention 2 spacer and cathode The lithium rechargeable battery of component.It should be noted that the nonaqueous electrolytic solution other than nonaqueous electrolytic solution secondary battery spacer The inscape of secondary cell is not limited to the inscape of following the description.
The nonaqueous electrolytic solution secondary battery of an embodiment of the invention usually has and will be infiltrated to following structure The battery element of electrolyte encloses the structure in housing material, and the structure is by cathode with anode folder across the present invention's The nonaqueous electrolytic solution secondary battery spacer of one embodiment is facing.Nonaqueous electrolytic solution secondary battery is preferably non-water power Solve electrolitc secondary cell, particularly preferably lithium rechargeable battery.It should be noted that so-called doping, refers to occluding, supporting, inhaling It is attached or be inserted into, refer to the phenomenon that lithium ion enters in the active materials of the electrodes such as anode.
The nonaqueous electrolytic solution secondary battery component of an embodiment of the invention is due to having one of present invention implementation The nonaqueous electrolytic solution secondary battery spacer of mode, therefore after being fitted into nonaqueous electrolytic solution secondary battery, this can be inhibited The increase of resistance after the charge and discharge cycles of nonaqueous electrolytic solution secondary battery.The nonaqueous electrolytic solution of an embodiment of the invention Secondary cell is due to having one of the present invention that the ion of per unit film thickness is adjusted to specific range through the value of energy barrier The nonaqueous electrolytic solution secondary battery spacer of embodiment, therefore play the excellent effect of cycle characteristics.
＜ anodes ＞
Nonaqueous electrolytic solution secondary battery component and nonaqueous electrolytic solution secondary battery as an embodiment of the invention Anode, as long as the component used usually as the anode of nonaqueous electrolytic solution secondary battery, there is no particular limitation, for example may be used Having the structure for being formed with the active material layer comprising positive active material and binder resin on the current collector just to use Pole piece.It should be noted that above-mentioned active material layer can also include conductive agent and/or sticking agent.
As above-mentioned positive active material, for example, the material of doped lithium ion can be adulterated.As this Material, specifically, for example, including the lithium composite xoide of the transition metal such as at least one kind of V, Mn, Fe, Co and Ni.
As above-mentioned conductive agent, for example, natural graphite, artificial graphite, coke class, carbon black, pyrolysis carbons, carbon Carbonaceous materials such as fiber and organic high molecular compound sintered body etc..Above-mentioned conductive agent can be used only a kind, and can also combine makes Use two or more.
As above-mentioned sticking agent, for example, the fluorine resins such as polyvinylidene fluoride, acrylic resin and benzene Ethylene-butylene rubber.It should be noted that sticking agent also has the function as thickener.
As above-mentioned positive electrode collector, for example, the conductors such as Al, Ni and stainless steel.Wherein, due to being easily worked For film, cheap, therefore more preferable Al.
The manufacturing method of anode as sheet, for example, positive active material, conductive agent and sticking agent are existed The method being press-formed on positive electrode collector；Using organic solvent appropriate by positive active material, conductive agent and sticking agent system After paste, which is distributed on positive electrode collector, is pressurizeed after dry and is bonded to the method on positive electrode collector； Deng.
＜ cathode ＞
Nonaqueous electrolytic solution secondary battery component and nonaqueous electrolytic solution secondary battery as an embodiment of the invention Cathode, as long as component used in cathode usually as nonaqueous electrolytic solution secondary battery, there is no particular limitation, for example The cathode for the structure for being formed with the active material layer comprising negative electrode active material and binder resin on the current collector can be used Piece.It should be noted that above-mentioned active material layer can also include conductive agent.
As above-mentioned negative electrode active material, for example, the material of doped lithium ion, lithium metal can be adulterated Or lithium alloy etc..As the material, for example, carbonaceous material etc..As carbonaceous material, natural graphite, people can be enumerated Make graphite, coke class, carbon black and pyrolysis carbons etc..
As above-mentioned negative electrode collector, for example, the electric conductors such as Cu, Ni and stainless steel, especially because lithium from It is difficult to form alloy with lithium in sub- secondary cell and be easily worked as film, therefore more preferable Cu.
The manufacturing method of cathode as sheet, for example, negative electrode active material is pressurizeed on negative electrode collector Molding method；After paste is made in negative electrode active material using organic solvent appropriate, which is distributed in negative electrode collector On, it is pressurizeed after dry and is bonded to the method on negative electrode collector；Deng.Preferably comprised in above-mentioned paste above-mentioned conductive agent, And above-mentioned sticking agent.
＜ nonaqueous electrolytic solutions ＞
As long as the nonaqueous electrolytic solution of the nonaqueous electrolytic solution secondary battery of an embodiment of the invention is that typically in non-aqueous Nonaqueous electrolytic solution used in electrolyte secondary batteries, there is no particular limitation, can be used for example and be dissolved in lithium salts Nonaqueous electrolytic solution made of in solvent.As lithium salts, for example, LiClO4、LiPF6、LiAsF6、LiSbF6、LiBF4、 LiCF3SO3、LiN(CF3SO2)2、LiC(CF3SO2)3、Li2B10Cl10, lower aliphatic carboxylic acid's lithium salts and LiAlCl4Deng.Above-mentioned lithium Salt can be used only a kind, two or more can also be applied in combination.
As the organic solvent for constituting nonaqueous electrolytic solution, for example, carbonates, ethers, esters, nitrile, amide Class, carbamates and sulfur-containing compound and imported into these organic solvents it is fluorine-based made of fluorine-containing organic solvent etc.. Above-mentioned organic solvent can be used only a kind, two or more can also be applied in combination.
The manufacturing method ＞ of ＜ nonaqueous electrolytic solution secondary batteries component and nonaqueous electrolytic solution secondary battery
The manufacturing method of nonaqueous electrolytic solution secondary battery component as an embodiment of the invention, such as can be with It enumerates and configures in order above-mentioned positive, an embodiment of the invention nonaqueous electrolytic solution secondary battery spacer and bear The method of pole.
In addition, the manufacturing method of the nonaqueous electrolytic solution secondary battery as an embodiment of the invention, such as in profit After forming nonaqueous electrolytic solution secondary battery component in aforementioned manners, which is put into component becomes In the container of the shell of nonaqueous electrolytic solution secondary battery, then, after being full of with nonaqueous electrolytic solution in the container, in the same of decompression Shi Jinhang is closed, it is possible thereby to manufacture the nonaqueous electrolytic solution secondary battery of an embodiment of the invention.
[embodiment]
Hereinafter, using Examples and Comparative Examples, the present invention is described in more detail, however the present invention is not limited to this A little embodiments.
[assay method]
Using the following method, determine physical property of the polyolefin porous membrane manufactured in Examples and Comparative Examples etc. and The cycle characteristics of nonaqueous electrolytic solution secondary battery.
(1) film thickness (unit：μm)：
Polyolefin porous membrane is determined using the high accuracy number calibrator (VL-50) of M Co., Ltd. itutoyo Film thickness.
(2) air permeability (unit：sec/100mL)：
The air permeability of polyolefin porous membrane is determined according to JIS P8117.
(3) ion of per unit film thickness penetrates energy barrier (unit：J/mol/μm)
Polyolefin porous membrane is cut into the discoid of φ 17mm, is sandwiched with the SUS plates of 2 thickness 0.5mm, φ 15.5mm, It injects electrolyte and button cell (CR2032 types) is made.Electrolyte has been used in ethylene carbonate (EC)/methyl ethyl carbonate herein The in the mixed solvent of ester (EMC)/diethyl carbonate (DEC)=3/5/2 (volume ratio) is so that LiPF6Concentration reach 1mol/L's Mode is dissolved with LiPF6Solution.
By made button cell be set to it is aftermentioned be set as in the thermostat of given temperature, use Solartron corporation AC impedances device (FRA 1255B) and CellTest systems (1470E), with frequency 1MHz~ 0.1Hz, voltage amplitude 10mV calculate nyquist diagram, and the liquid of polyolefin porous membrane at each temperature is found out according to the value of X intercepts Bulk resistor (liquid resistance) r0, calculate ion using following formulas (1) and (2) and penetrate energy barrier.The temperature of thermostat is set as 50 DEG C, 25 DEG C, 5 DEG C, -10 DEG C.
Herein, ion is indicated through energy barrier following formula (1).
K=1/r0=Aexp (- Ea/RT) (1)
Ea：Ion penetrates energy barrier (J/mol)
k：Reaction constant
r0：Liquid resistance (Ω)
A：Frequency factor
R：Gas constant=8.314J/mol/K
T：The temperature (K) of thermostat
Become following formula (2) if the natural logrithm on the both sides of modus ponens (1).Based on the formula (2), the inverse of temperature is drawn ln(1/r0), and find out as by the drafting desire to make money or profit the straight line obtained with least square method slope-Ea/R, in-Ea/R Value on be multiplied by gas constant R and calculate Ea.Thereafter, by the Ea of calculating divided by the film thickness of polyolefin porous membrane, per unit is calculated The ion of film thickness penetrates energy barrier.
Ln (1/k)=ln (1/r0)=lnA-Ea/RT (2)
(4) cycle characteristics
Using method shown in process below (A)~process (E), determine manufactured in embodiment, comparative example it is non- The cycle characteristics of water electrolysis liquid secondary battery, specifically, determining the electrode resistance increment rate after 100 cycles.Hereinafter, right It is shown in detail in process (B) in the calculation method of electrode resistance.
(A) initial charge/discharge is tested
To used the nonaqueous electrolytic solution secondary battery spacer manufactured in embodiment, comparative example without passing through charge and discharge The new nonaqueous electrolytic solution secondary battery of electricity cycle, to carry out the CC- of charging current value 0.2C in 2.7~4.1V of voltage range CV chargings (terminate current condition 0.02C), the CC electric discharges of discharge current value 0.2C (by with 1 hour to the electric discharge based on 1 hour rate The current value that the rated capacity of capacity is discharged is set as 1C, also identical below) as 1 cycle, it implements 4 at 25 DEG C and follows The initial charge/discharge of ring.So-called CC-CV charging herein is following charging method, that is, filled with the constant electric current set Electricity maintains its voltage after reaching given voltage while reducing electric current.In addition so-called CC electric discharges, to set Constant current discharge to given voltage method, it is also identical below.
(B) initial electrode resistance R1Measurement
After the experiment of above-mentioned initial charge/discharge, using setting motor LCR tester (trade names day：Chemical impedance tester： Model 3532-80), in 25 DEG C of room temperature, voltage amplitude 10mV is applied to nonaqueous electrolytic solution secondary battery, calculates nyquist diagram (ナイキストプロット).Resistance value after being tested as initial charge/discharge, by above-mentioned nyquist diagram and the intersection point of X-axis, i.e. X intercepts are as liquid resistance R0And the resistance value R of the real part of measurinng frequency 10Hz10HzIt reads, calculates R10Hz- R0, as R1。 R herein1Indicate initial electrode resistance.
(C) charge and discharge of 100 cycles
It is connected on after process (B), to carry out the CC-CV chargings of charging current value 1C in 2.7~4.2V of voltage range (eventually Only current condition 0.02C), the CC of discharge current value 10C electric discharge as 1 cycle, the charge and discharges of 100 cycles are implemented at 55 DEG C Electricity.
(D) the electrode resistance R ' after 100 cycles1Measurement
Determine the liquid resistance R after 100 cycles in the same manner with process (B)0(100cyc)And the survey after 100 cycles Determine the resistance value R of the real part of frequency 10Hz10Hz(100cyc), the electrode resistance after 100 cycles is calculated based on formula below (3) R’1。
R’1=R10Hz(100cyc)- R0(100cyc) (3)
(E) the electrode resistance increment rate after 100 cycles
According to the R determined in process (B)1Value and process (D) in the R ' that determines1Value, be based on formula below (4), Calculate the electrode resistance increment rate after 100 cycles.
R’1/R1* the electrode resistance increment rate (%) (4) after 100=100 cycle
It should be noted that 100 cycle after electrode resistance increment rate be 100% mean with before charge and discharge cycles Electrode resistance (initial electrode resistance R1) compared to 100 cycle after electrode resistance do not change.Electricity after being recycled at 100 Electrode resistance increment rate is more than in the case of 100%, it is meant that the electrode resistance after 100 cycles and the electrode before charge and discharge cycles Resistance is compared to increase.
[embodiment 1]
[manufacture of nonaqueous electrolytic solution secondary battery spacer]
Prepare ultra-high molecular weight polyethylene powder (Hi-Zex-Million 145M, Mitsui Chemicals, Inc's system) 18 Parts by weight and in the structure Petropols (the alicyclic saturated hydrocarbon resin of 125 DEG C of softening point) 2 weights with multiple tertiary hydrogen atoms Measure part.The grain size that these powder are crushed to powder with blender is identical and mix, and obtains mixture 1.
Then, mixture 1 is added to from quantitative feeder in twin shaft kneading machine and carries out melting mixing.At this point, will The temperature inside twin shaft kneading machine before input atoleine is set as 150 DEG C, is added 80 parts by weight side of atoleine with pump Expect in twin shaft kneading machine.It should be noted that so-called " temperature inside twin shaft kneading machine ", refers to the area in twin shaft kneading machine The temperature of the part of the inside machine barrel of segment type.The machine barrel of sector type is the machine for the block type for referring to link with arbitrary length Cylinder.
Thereafter, it is squeezed out from the T shape die heads for being set as 210 DEG C with sheet by gear pump, the vistanex of sheet is made Composition 1.The polyolefine resin composition 1 of squeezed out sheet is set to embrace on chill roll and be cooled to.After cooling, to sheet Polyolefine resin composition 1 carry out in the MD direction with 6.4 times stretch after, on the directions TD with 6.0 times stretch gradually drawing It stretches, obtains stretched polyolefine resin composition 2.
After being cleaned with cleaning solution (dichloromethane) to stretched polyolefine resin composition 2, dried in 133 DEG C of ventilations 25 minutes are stood in case, the drying heat fixation of the piece (polyolefine resin composition of sheet) after thus being cleaned obtains Polyolefin porous membrane.Using the polyolefin porous membrane of gained as polyolefin porous membrane 1.It regard polyolefin porous membrane 1 as non-water power Solve liquid secondary battery spacer 1.
Thereafter, using above-mentioned assay method, the physical property of the polyolefin porous membrane 1 of gained is determined.Polyolefin porous membrane 1 Film thickness be 13 μm, air permeability 156sec/100mL.In addition, the physical property table of the polyolefin porous membrane 1 determined is shown in table 1 In.
[making of nonaqueous electrolytic solution secondary battery]
(positive making)
It has used by by LiNi0.5Mn0.3Co0.2O2/ conductive agent/PVDF (weight ratio 92/5/3) be coated on aluminium foil and The commercially available anode of manufacture.For above-mentioned commercially available anode, so that the size for being formed with the part of positive electrode active material layer is 40mm × 35mm and in its periphery in such a way that width 13mm residual does not form the part of positive electrode active material layer, cut out Aluminium foil and anode is made.The thickness of positive electrode active material layer is 58 μm, density 2.50g/cm3。
(making of cathode)
It has used by by graphite/styrene -1,3-butadiene copolymer/sodium carboxymethylcellulose (weight ratio 98/1/ 1) the commercially available cathode for being coated on copper foil and manufacturing.For above-mentioned commercially available cathode, so as to be formed with negative electrode active material layer The size of part be 50mm × 40mm and do not form the portion of negative electrode active material layer with width 13mm residual in its periphery The mode divided, cuts out copper foil and cathode is made.The thickness of negative electrode active material layer is 49 μm, density 1.40g/cm3。
(assembling of nonaqueous electrolytic solution secondary battery)
Using above-mentioned anode, above-mentioned cathode and nonaqueous electrolytic solution secondary battery spacer 1, method as shown below is utilized Produce nonaqueous electrolytic solution secondary battery.
In composite membrane Soft Roll, stack gradually (configuration) above-mentioned anode, nonaqueous electrolytic solution secondary battery spacer 1, with And cathode, thus obtain nonaqueous electrolytic solution secondary battery component 1.At this point, so that the interarea of the positive electrode active material layer of anode Whole be contained in cathode negative electrode active material layer interarea range in (Chong Die with interarea) mode, be configured with anode and Cathode.
Next, the stacking aluminium layer that nonaqueous electrolytic solution secondary battery is packed into pre-production with component 1 is formed with hot sealing layer Bag in, then nonaqueous electrolytic solution 0.25mL is added into the bag.Above-mentioned nonaqueous electrolytic solution is by ethylene carbonate, methyl ethyl carbonate Ester, diethyl carbonate are with 3：5：The in the mixed solvent that 2 (volume ratios) mix dissolves LiPF in a manner of reaching 1mol/L6And It prepares.Hereafter, while decompression in by bag, which is sealed, thus produces nonaqueous electrolytic solution secondary battery 1.
Thereafter, cycle characteristics, i.e. 100 for the nonaqueous electrolytic solution secondary battery 1 that profit obtains with the aforedescribed process have been carried out The measurement of electrode resistance increment rate (%) after cycle.It the results are shown in table 1.
[embodiment 2]
[manufacture of nonaqueous electrolytic solution secondary battery spacer]
In addition to the temperature that will be put into twin shaft kneading machine inside the twin shaft kneading machine before atoleine is set as 150 DEG C, heptane is used as cleaning solution, in the dry heat that 133 DEG C carried out the piece cleaned with cleaning solution (heptane) with 15 minutes Other than fixation, polyolefin porous membrane is obtained using method same as Example 1.The polyolefin porous membrane of gained is set as polyene Hydrocarbon perforated membrane 2.It regard polyolefin porous membrane 2 as nonaqueous electrolytic solution secondary battery spacer 2.
Thereafter, using above-mentioned assay method, the physical property of the polyolefin porous membrane 2 of gained is determined.Polyolefin porous membrane 2 Film thickness be 16 μm, air permeability 113sec/100mL.In addition, the physical property table of the polyolefin porous membrane 2 determined is shown in table 1 In.
[making of nonaqueous electrolytic solution secondary battery]
Nonaqueous electrolytic solution secondary battery spacer has been used in addition to substitution nonaqueous electrolytic solution secondary battery spacer 1 Other than 2, nonaqueous electrolytic solution secondary battery is produced same as Example 1ly.Made nonaqueous electrolytic solution secondary battery is set For nonaqueous electrolytic solution secondary battery 2.
Thereafter, profit with the aforedescribed process, has carried out cycle characteristics, i.e. 100 of the nonaqueous electrolytic solution secondary battery 2 of gained The measurement of electrode resistance increment rate (%) after cycle.It the results are shown in table 1.
[embodiment 3]
[manufacture of nonaqueous electrolytic solution secondary battery spacer]
In addition to the temperature that will be put into twin shaft kneading machine inside the twin shaft kneading machine before atoleine is set as 150 DEG C, heptane is used as cleaning solution, in the dry heat that 120 DEG C carried out the piece cleaned with cleaning solution (heptane) with 1 minute Other than fixation, polyolefin porous membrane is obtained using method same as Example 1.The polyolefin porous membrane of gained is set as polyene Hydrocarbon perforated membrane 3.It regard polyolefin porous membrane 3 as nonaqueous electrolytic solution secondary battery spacer 3.
Thereafter, using above-mentioned assay method, the physical property of the polyolefin porous membrane 3 of gained is determined.Polyolefin porous membrane 3 Film thickness be 18 μm, air permeability 118sec/100mL.In addition, the physical property table of the polyolefin porous membrane 3 determined is shown in table 1 In.
[making of nonaqueous electrolytic solution secondary battery]
Nonaqueous electrolytic solution secondary battery spacer has been used in addition to substitution nonaqueous electrolytic solution secondary battery spacer 1 Other than 3, nonaqueous electrolytic solution secondary battery is produced same as Example 1ly.Made nonaqueous electrolytic solution secondary battery is set For nonaqueous electrolytic solution secondary battery 3.
Thereafter, profit with the aforedescribed process, has carried out cycle characteristics, i.e. 100 of the nonaqueous electrolytic solution secondary battery 3 of gained The measurement of electrode resistance increment rate (%) after cycle.It the results are shown in table 1.
[embodiment 4]
[manufacture of nonaqueous electrolytic solution secondary battery spacer]
In addition to the temperature that will be put into twin shaft kneading machine inside the twin shaft kneading machine before atoleine is set as 150 DEG C, heptane is used as cleaning solution, in the dry heat that 100 DEG C carried out the piece cleaned with cleaning solution (heptane) with 8 minutes Other than fixation, polyolefin porous membrane is obtained using method same as Example 1.The polyolefin porous membrane of gained is set as polyene Hydrocarbon perforated membrane 4.It regard polyolefin porous membrane 4 as nonaqueous electrolytic solution secondary battery spacer 4.
Thereafter, using above-mentioned assay method, the physical property of the polyolefin porous membrane 4 of gained is determined.Polyolefin porous membrane 4 Film thickness be 17 μm, air permeability 124sec/100mL.In addition, the physical property table of the polyolefin porous membrane 4 determined is shown in table 1 In.
[making of nonaqueous electrolytic solution secondary battery]
Nonaqueous electrolytic solution secondary battery spacer has been used in addition to substitution nonaqueous electrolytic solution secondary battery spacer 1 Other than 4, nonaqueous electrolytic solution secondary battery is produced same as Example 1ly.Made nonaqueous electrolytic solution secondary battery is set For nonaqueous electrolytic solution secondary battery 4.
Thereafter, profit with the aforedescribed process, has carried out cycle characteristics, i.e. 100 of the nonaqueous electrolytic solution secondary battery 4 of gained The measurement of electrode resistance increment rate (%) after cycle.It the results are shown in table 1.
[embodiment 5]
[manufacture of nonaqueous electrolytic solution secondary battery spacer]
In addition to using the ester ring type of 90 DEG C of softening point to be saturated as the Petropols in the structure with multiple tertiary hydrogen atoms The temperature that will be put into twin shaft kneading machine inside the twin shaft kneading machine before atoleine is set as by 2 parts by weight of hydrocarbon resin 144 DEG C, heptane is used as cleaning solution, the dry of the piece cleaned with cleaning solution (heptane) has been carried out with 15 minutes at 134 DEG C Other than scorching fixation, polyolefin porous membrane is obtained using method same as Example 1.The polyolefin porous membrane of gained is set For polyolefin porous membrane 5.It regard polyolefin porous membrane 5 as nonaqueous electrolytic solution secondary battery spacer 5.
Thereafter, using above-mentioned assay method, the physical property of the polyolefin porous membrane 5 of gained is determined.Polyolefin porous membrane 5 Film thickness be 13 μm, air permeability 127sec/100mL.In addition, the physical property table of the polyolefin porous membrane 5 determined is shown in table 1 In.
[making of nonaqueous electrolytic solution secondary battery]
Nonaqueous electrolytic solution secondary battery spacer has been used in addition to substitution nonaqueous electrolytic solution secondary battery spacer 1 Other than 5, nonaqueous electrolytic solution secondary battery is produced same as Example 1ly.Made nonaqueous electrolytic solution secondary battery is set For nonaqueous electrolytic solution secondary battery 5.
Thereafter, profit with the aforedescribed process, has carried out cycle characteristics, i.e. 100 of the nonaqueous electrolytic solution secondary battery 5 of gained The measurement of electrode resistance increment rate (%) after cycle.It the results are shown in table 1.
[embodiment 6]
[manufacture of nonaqueous electrolytic solution secondary battery spacer]
In addition to using the ester ring type of 90 DEG C of softening point to be saturated as the Petropols in the structure with multiple tertiary hydrogen atoms The temperature that will be put into twin shaft kneading machine inside the twin shaft kneading machine before atoleine is set as by 2 parts by weight of hydrocarbon resin 144 DEG C, heptane is used as cleaning solution, in the drying that 120 DEG C carried out the piece cleaned with cleaning solution (heptane) with 1 minute Other than heat fixation, polyolefin porous membrane is obtained using method same as Example 1.The polyolefin porous membrane of gained is set as poly- Alkene perforated membrane 6.It regard polyolefin porous membrane 6 as nonaqueous electrolytic solution secondary battery spacer 6.
Thereafter, using above-mentioned assay method, the physical property of the polyolefin porous membrane 6 of gained is determined.Polyolefin porous membrane 6 Film thickness be 22 μm, air permeability 126sec/100mL.In addition, the physical property table of the polyolefin porous membrane 6 determined is shown in table 1 In.
[making of nonaqueous electrolytic solution secondary battery]
Nonaqueous electrolytic solution secondary battery spacer has been used in addition to substitution nonaqueous electrolytic solution secondary battery spacer 1 Other than 6, nonaqueous electrolytic solution secondary battery is produced same as Example 1ly.Made nonaqueous electrolytic solution secondary battery is set For nonaqueous electrolytic solution secondary battery 6.
Thereafter, profit with the aforedescribed process, has carried out cycle characteristics, i.e. 100 of the nonaqueous electrolytic solution secondary battery 6 of gained The measurement of electrode resistance increment rate (%) after cycle.It the results are shown in table 1.
[comparative example 1]
[manufacture of nonaqueous electrolytic solution secondary battery spacer]
In addition to by ultra-high molecular weight polyethylene powder (Hi-Zex-Million 145M, Mitsui Chemicals, Inc's system) 20 parts by weight are set as, Petropols are not added with, will will be put into twin shaft kneading machine in the twin shaft kneading machine before atoleine The temperature in portion is set as 134 DEG C, and heptane is used as cleaning solution, with 1 minute cleaned with cleaning solution (heptane) at 120 DEG C Piece drying heat fixation other than, using method same as Example 1 obtain polyolefin porous membrane.By the polyene of gained Hydrocarbon perforated membrane is set as polyolefin porous membrane 7.It regard polyolefin porous membrane 7 as nonaqueous electrolytic solution secondary battery spacer 7.
Thereafter, the physical property of the polyolefin porous membrane 7 obtained using above-mentioned assay method is determined.Polyolefin porous membrane 7 Film thickness be 24 μm, air permeability 165sec/100mL.The physical property table of the polyolefin porous membrane 7 determined is shown in Table 1.
[making of nonaqueous electrolytic solution secondary battery]
Nonaqueous electrolytic solution secondary battery spacer has been used in addition to substitution nonaqueous electrolytic solution secondary battery spacer 1 Other than 7, nonaqueous electrolytic solution secondary battery is produced same as Example 1ly.Made nonaqueous electrolytic solution secondary battery is set For nonaqueous electrolytic solution secondary battery 7.
Thereafter, cycle characteristics, i.e. 100 for the nonaqueous electrolytic solution secondary battery 7 that profit obtains with the aforedescribed process have been carried out The measurement of electrode resistance increment rate (%) after cycle.It the results are shown in table 1.
[result]
By the nonaqueous electrolytic solution secondary battery manufactured in Examples 1 to 6, comparative example 1 with spacer (polyolefin porous membrane) Physics value and Examples 1 to 6, comparative example 1 in electrode resistance after 100 of nonaqueous electrolytic solution secondary battery cycles manufacturing Increment rate (%) is recorded in table 1 below.
[table 1]
[conclusion]
By the record of table 1 it is found that enclose the ion of per unit film thickness through energy barrier be 300J/mol/ μm or more and The nonaqueous electrolytic solution secondary battery manufactured in 900J/mol/ μm of Examples 1 to 6 below spacer (polyolefin porous membrane) Nonaqueous electrolytic solution secondary battery penetrates energy barrier to be made in the comparative example 1 outside above-mentioned range with the ion for enclosing per unit film thickness The nonaqueous electrolytic solution secondary battery of the nonaqueous electrolytic solution secondary battery made spacer is compared, the electrode resistance after 100 cycles Increment rate is low, and cycle characteristics is more excellent.
Industrial availability
As described above, having the non-water power of the nonaqueous electrolytic solution secondary battery spacer of an embodiment of the invention The cycle characteristics for solving liquid secondary battery is excellent.Therefore, it is possible to by the non-aqueous electrolyte secondary electricity of an embodiment of the invention The component that spacer is used in pond as nonaqueous electrolytic solution secondary battery effectively utilizes.

Claims (4)

1. a kind of nonaqueous electrolytic solution secondary battery spacer is that the nonaqueous electrolytic solution secondary battery comprising polyolefin porous membrane is used Spacer,
The ion of per unit film thickness is 300J/mol/ μm or more and 900J/mol/ μm or less through energy barrier.
2. nonaqueous electrolytic solution secondary battery spacer according to claim 1, in polyolefin porous membrane one side Or two sides has insulating properties porous layer.
3. a kind of nonaqueous electrolytic solution secondary battery component, to configure in order anode, non-water power as claimed in claim 1 or 2 Solution liquid secondary battery is formed with spacer and cathode.
4. a kind of nonaqueous electrolytic solution secondary battery has nonaqueous electrolytic solution secondary battery interval as claimed in claim 1 or 2 Part.
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KR20180121847A (en) 2018-11-09
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